New carboxylic acids of the fatty-aromatic series and process of making same



Patented Dec. 15, 1931 UNITED STATES PATENT. OFFICE GEOBG KALISOHER ANDHEINZ O! IRANKFORT-ON-THE-HAIN, GERMANY, ASSIGNOBSRBY IFSNE ASSIGNMENTS,.l'O wm'nmor CHEMICAL COMTANY, 1110., OF NEW YORK, N. Y, A CORPORATIONOF NEW YORK msw cmnomro ACIDS or ran ram-mourn exams AND rnocass or mumIo Drawing. Original appiication fled July 9, 1927, Serial No. 204,600,and in Germany August 11, 1828. Divided and this application filed June5, 1928. Serial No. 288,127.

This application is a division of our pending-application Serial No.204,660, filed Our invention relates to new carboxylic acids of thefatty-aromatic series, which are obtained by heating an unsaturated acidcompound of the type V x x doon wherein the Xs mean hydrogen atoms,which may be replaced by a .monovalent substituent such as halogen,akyl, aryl, a-ralkyl, a

further carboxylic oup etc., with polycyclic aromatic hydrocar onscontaining more than two condensed nuclei, or their substitutionproducts, particularly with trinuclear aromatic hydrocarbons. Forobtaining pure condensation products in a good yield it may beadvantageous to carry out the reaction with addition of an acidcondensing agent such as a hydrogenhalide acid or aluminium chloride andfor homogenizing the mass of reaction. In some cases it is advisable towork in presence of a diluent. We have further found that instead ofusing the unsaturated acids themselves one may start from their hydrogenhalide addition products being often more easily obtainable, whichcompounds under the conditions applied in the course of the reaction areconverted into the corresponding olefinic carboxylic acids hydrogenhalide being split off. In consequence thereof e. g. the samecondensation products are obtained when using for the process theacrylic acid as well as aand ,B-chloropropionic acid.

In the reaction of the new process the double bond of the unsaturatedcarboxylic acids probably joins with adouble bond of the aromatichydrocarbon applied.

As polycyclic aromatic hydrocarbons appropriated for the processanthracene, phenanthrene, chrysene and their substitution products maybe named, containing in the nuclei one or more nonreactive substituentssuch as halo ens, alkyl,-hydroxy-, alkoxy-, aryloxy-, ara kyloxy groupsetc.; among the unsaturated acid compounds of the aforesaid type ortheir equivalent hydrogen halide addition products one may use for ourprocess e. g. the acrylic acid, the ocand ,B-chloropropionic acid, theirhomologues and substitution products, such as crotonic acid,chloroacrylic and chlorocrotonic acid, further the arylacrylic acids,their homologues and substitution roducts such as phenylacrylic acidhydroxyp enylacrylic acid. As starting materials containing a furthercarboxylic group in their molecule, the maleic acid, the chlorosuccinicacid, etc., may be used. Instead of the carboxylic acids compoundsreacting like them such as the acid halides, esters anhydrides and thelike may be used for the process.

The new carboxylic acids of the fatty-aromatic series are when drywhitish to feebly colored crystalline powders, having a definite meltingpoint, being soluble in organic solvents, forming metal salts'andderivatives, such as esters, anhydrides, chlorides, most of them beingcharacterized by a characteristic fluorescence of their solutions inalcohol as well as of the aqueous solutions of their sodium salts. Theymay be used as intermediates for the production of dyestufl's andpharmaceutical products.

In order to further illustrate our invention the following examples aregiven, the parts being by'weight and all temperatures in centigradedegrees, but it is understood, that our invention is not limited to theparticular products or reacting conditions mentioned therein.

Example 1 At about 110 2 parts of anthracene are suspended in 7 parts ofacrylic acid and while increasing the temperature slowly to about 170 acurrent of hydrochloric acid gas is introduced into the mixture for somehours. After cooling down the mass is poured into water and theprecipitate is filtered, dissolved in a caustic alkali solution andprecipitated again by acidifying the alkaline solution.

I The new compound thus obtained corresponds probably to the formula /l\H-C-H It is easily soluble in the usual organic solvents, its solutionin alcohol shows a blue fluorescence, it melts at 187188 when recrystallized from benzene. It forms a Well defined crystalline sodiumsalt, difiicultly soluble in water, characterized by a blue fluorescenceof its aqueous solutions.

Example 2 A solution of 2 parts of anthracene and 5 parts of,B-chloropropionic acid in about 8 parts of dichlorobenzene is heated tothe boiling point for about 5 hours. After having resinous state, isdissolved in a caustic alkali solution and precipitated by acidifyingthis solution.

The new compound having probably the formula:

o1 rt-ix H-' ioooH is 'then obtained as a pure white powder, easilysoluble in most organic solvents, its alcoholic solution beingcharacterized by a blue fluorescence melting at 237 afterrecrystallization from glacial acetic acid.

By using other substitution products of anthracene such as halogenated,alkylated or hydroxyderivatives, similar products areobtained, e. g. byusing 1.5-dichloroanthracene, a colorless product, melting at 218 byusing 2.7 -dimethylanthracene, a nearly colorless product; melting atabout 205; by using 1- hydroxyanthracene a greyish colored prodnot isobtained soluble in the usual organic solvents and in a sodium carbonatesolution with a brownish color forming azocompounds when combined withdiazocompounds, e. g.

an orange yellow colored p-nitrobenzene.

When replacing anthracene by other condensed polycyclic aromatichydrocarbons, when condensing, for example, in an analogous manner 3parts of phenanthrene with 10 parts of chloropropionic acid, a newproduct with diazocarboxylic acid is obtained containing thephenanthrene residue and melting at 132 when recrystallized frombenzene. In the same manner its methyl-isopropylic homologue, i. e.retene, may be used for the process.-

We claim:

1. The process which comprises causing a trinuclear aromatic hydrocarbonto interact with a compound having the chemical constitution of ahydrogen halide additionprodnot of an olefinic carboxylic acid andcorresponding to the general formula:

CzXaHY O OH wherein X represents hydrogen, halogen, alkyl, aryl, aralkylor a further carboxylic acid group and Y represents a halogen.

2. The process which comprises causing a. trinuclear aromatichydrocarbon to interact with a compound having the chemical constitutionof a hydrogen halide addition product of an olefinic carboxylic acid andcorresponding to the general formula:

wherein X represents hydrogen or aryl and Y represents a halogen.

3. The process which comprises causing a trinuclear aromatic hydrocarbonto interact with a compound having the .chemical constitution of ahydrogen halide addition product of an olefinic carboxylic acid andcorresponding to the general formula:

CgH X OOH wherein X represents hydrogen or aryl and Y represents ahalogen.

4. The process which comprises causing a compound of the anthraceneseries to interact with a compound having the chemical constitution of ahydrogen halide addition product of an olefinic carboxylic acid andcorresponding to the general formula:

0011 wherein X represents hydrogen or aryl and Y represents a halogen.

5. The process which comprises causing a.

compound of the anthracene series to interact in presence-of a diluentwith a compound having the chemical constitution of a hydrogen halideaddition product of an olefinic carboxylic acid and corresponding to thegeneral formula:

OOH wherein X represents hydrogen or aryl and Y represents a halogen. 56. The process which comprises causing La compound of the anthraceneseries to interact with ,B-chloropropionic acid.

In testimony whereof we aflix our signatures. GEORG KALISGHER.

HEINZ SCHEYER.

